Method for cathodic electrodeposition of coating compositions containing diels-alder adducts

ABSTRACT

Described herein is an organic coating composition particularly useful in cathodic electrodeposition comprising a dispersion, solution or suspension of a coating composition characterized by (a) a reaction product of a conjugated fatty acid ester and an acrylic containing monomer, preferably containing oxirane rings; and (b) Formula A within the molecule, being the reaction product of reacting an oxirane ring and an amine; wherein Formula A is: 
     
         --CH.sub.2 --C(Z)--CH.sub.2 --N═ 
    
     wherein Z is hydrogen, hydroxyl, alkoxy of 1 to 6 carbon atoms; acyloxy of from 1 to 6 carbon atoms; (═O, as in a ketone), --OR&#39;-- n  H; --OR&#39;-- n  OH, and --OR&#39;(CH 2  OH)-- n  OH, wherein R&#39; is a saturated alkylene group of from 2 to 4 carbon atoms and n is a number from 1 to 6. 
     Also described is a method of electrodepositing coating compositions containing said adducts onto a cathode.

BACKGROUND OF THE INVENTION

It has become commercially of significance to employ cathodicelectrodeposition coating compositions for improved corrosion resistancecan be obtained employing said compositions.

U.S. Pat. No. 4,001,101 teaches the electrodeposition of epoxycompositions which contain boron in the form of boric acid and likecompounds. U.S. Pat. No. 4,001,156 teaches a method of producing epoxygroup containing quaternary ammonium salt containing resins.

SUMMARY OF THE INVENTION

An object of the present invention is coating compositions of improvedcorrosion resistance particularly when employed in the cathodicelectrodeposition coating process. Additionally the compositions whencured have improved weather durability, particularly on exposure tosunlight and ultraviolet light. There is an improvement over prior artcompositions in chaulking resistance, weather exposure and lower baketemperatures.

The coating compositions of the present invention are prepared byreacting through the double bonds of the reactants an acrylic materialcontaining an oxirane ring with a conjugated fatty acid ester. Withoutbeing bound to any particular theory, it is believed that this reactionis a Diels-Alder adduct reaction. The product of that reaction is inturn reacted with an amine to introduce the nitrogen moiety into themolecule.

DESCRIPTION OF PREFERRED EMBODIMENTS

In the preparation of the products to be used in the process of thepresent invention, the first step is the Diels-Alder reaction betweenthe conjugated fatty acid esters and monomeric materials containingoxirane ring. The reaction can be said to proceed along the followinglines: ##STR1## wherein R and R₁ are residue of fatty acid estermolecule; R₂ and R₃ are residue of fatty acid ester molecule; R₂ and R₃are residue of acrylic containing monomer.

Catalysts may be used to accelerate the adduct reaction such asperoxides.

Reference may be made to applicant's concurrently filed case U.S. Ser.No. 859,295, filed Dec. 12, 1977, CATHODIC ELECTRODEPOSITIONCOMPOSITIONS EMPLOYING FATTY ACID DERIVATIVES.

The reactants that are employed for the conjugated fatty acid componentmay be exemplified by the following materials: alkyl esters wherein thealkyl group ranges from 1 to 12 carbon atoms and the fatty acid that maybe employed are long chain fatty acids having from 8 to 24 carbon atoms.A preferred fatty acid is one having high conjugated diene concentrationsuch as products available under the name Pamolyn (trademark ofHercules) especially Pamolyn 380 which has a high concentration ofunsaturation at positions 9 and 11 of C₁₈ fatty acid. Suitable fattyacids are caprylic, capric, lauric, myristic, palmitic palmitoleic,stearic, oleic, ricinoleic, linoleic, linolenic, eleostearic, licanic,arachidic, arachidonic, behenic, clupanodonic, lignoceric, nisinic, andthe like. A preferred alcohol is an alkanol of from 1 to 8 carbon atoms,such as methanol, butanol, hexanol, and the like.

It is to be appreciated that the esters of the conjugated fatty acidsmay be employed by using the reaction products resulting from reactingconjugated fatty acids with polyols.

Exemplary among the polyols are the following: ethylene glycol,propylene glycol, butylene glycol, glycerol, trimethylolpropane,hexanetriol, pentaerythritol, neopentylglycol, trimethylolethane and thelike. In general the amount of alcohol added is sufficient to react allof the fatty acid so that the number of equivalents of hydroxyl groupsexceeds the number of equivalents of carboxyl groups in a range of1:1-1:1.3--carboxyl:hydroxyl groups.

The monomeric reactants that may be employed for the Diels-Alderreaction may be exemplified by the following materials: acrylic ormethacrylic materials alone or together with other monomeric materials.

By "acrylic" is meant a material containing therein the monomer of theformula:

    CH.sub.2 = C(B) C(O)--

wherein B=hydrogen, methyl or ethyl.

Exemplary acrylic materials that may be employed are acrylic ormethacrylic acids, the alkylesters or hydroxyalkylesters thereof wherethe alkyl group has from one to 18 carbon atoms, such as isobornylacrylate, methyl(meth)acrylate, butyl(meth)acrylate,2-ethylhexyl-(meth)acrylate, steryl acrylate, steryl methacrylate, andthe like, acrylamides, methacrylamides, and the like. It is to beappreciated that other copolymerizable monomers may also be reacted withthe acrylic material. Exemplary ethylenically unsaturated materials arestyrene, vinyl toluene; 3,5-dimethyl styrene, p-tertbutyl styrene, alphamethyl styrene, and the like, unsaturated dicarboxylic acids oranhydrides and the alkylesters thereof from 1 to 18 carbon atoms (suchas maleic anhydride, fumaric acid and the like.

A preferred class of acrylic reactants are those that contain theacrylic moiety together with an oxirane ring in the same molecule, suchas glycidyl acrylate and methacrylate and other similar type materialssuch as those taught in U.S. Pat. No. 3,773,855, which is herebyincorporated by reference, such as acrylic and methacrylic esters of themonoglycidyl ether of sulfonyl bisphenol, the monoglycidyl ether of a C₁to C₁₀ alkylene bisphenol, the monoglycidyl ether of oxybisphenol, themonoglycidyl ether of thiobisphenol, the monoglycidyl ether ofaminobisphenol and the monoglycidyl ether of α,α-bis(p-hydroxphenyl)tolylethane; the acrylic and methacrylic esters of3-oxy-6,7-epoxyheptanol, 3-aza-6,7-epoxyheptanol, or3-thia-6,7-epoxyheptanol; the reaction products of one mole of acrylicor methacrylic acid with one mole of polyphenylenesulfide diglicidylether, polyphenyleneamine diglicidyl ether, or polyphenyleneoxidediglycidyl ether; the reaction products of one mole of acrylic acid ormethacrylic acid with one mole of the polycondensation product ofepichlorohydrin with sulfonyl bis(phenylmercaptan) or sulfonylbisphenol; the reaction products of one mole of acrylic acid ormethacrylic acid with one mole of the poly-condensation product ofepichlorohydrin with α,α-bis(p-hydroxyphenyl) tolylethane orα,α-bis(p-thiophenyl) tolylethane; the acrylic and methacrylic esters ofpoly (C₁ -C₄ alkyleneoxide glycol) monoglycidyl ether; and the like.

The reaction parameters for Reaction No. 1 are to produce the reactionin the liquid state with or without a presence of an organic solventwhich is non-reactive with the reactants at a temperature ranging fromabout 150° C. to 250° C.

The second step in the reaction scheme is to react the Diels-Alderadduct which contains an oxirane ring with an amine containing an activehydrogen in order to open the oxirane ring present in the adduct. Thereaction scheme can be shown as follows: ##STR2## wherein R₄ is theresidue of the Diels-Alder adduct; and HNR₅ R₆ represents the aminereactants.

The product shown in Reaction No. 2 contains the moiety: --CH₂--CH(OH)--CH₂ --N< which is the expected result of reacting thesecondary amine with the oxirane ring. For further modification of thepolymer the hydroxyl group may be converted:

(a) to a ketone by reacting the product shown in reaction No. 2 with anoxidizing agent, such as permanganate, a chromic acid and the like, or

(b) to a hydrogen atom by means of a Grignard type reaction such as byreacting the product shown in reaction No. 2 with HBr to convert thehydroxyl group beta to the nitrogen atom to the bromide form; thenconverting the bromide to the Grignard reagent by reaction withmagnesium and then reacting that product with an alkanol such asmethanol or propanol; or

(c) to the alkoxy group by reaction with an alkyl halide; or

(d) to the acyloxy form by esterification with a carboxylic acid; or

(e) to the product containing --OR'--_(n) H by reaction with an alkyleneoxide of from two to four carbon atoms; or

(f) to --OR'(CH₂ OH)--_(n) OH by reacting with epihalohydrin and thelike and then converting to the hydroxyl form by hydrolysis; or

(g) to --OR'--_(n) OH by reaction with a glycol, and the like.

Therefore it can be said that the polymer contains Formula A which is ofthe structure:

    --CH.sub.2 --C(Z)--CH.sub.2 --N<

wherein Z is independently selected from the group consisting ofhydrogen, hydroxyl, alkyl ether or acyloxy wherein the alkyl and acylgroup have from 1 to 6 carbon atoms; (═O, as in a ketone, --OR'--_(n) H;--OR'--_(n) OH; and --OR'(CH₂ OH--_(n) OH; wherein R' is a saturatedalkylene group of from 2 to 4 carbon atoms and n is a number of from 1to 6.

Exemplary amines that may be used in Reaction No. 2 are those aminesthat contain a replaceable hydrogen, such as primary or secondary aminessuch as mono- or dialkylamine, mono- or di-alkanol amines and polyaminessuch as polyalkylene polyamines, etc. Useful amines are mono- ordi-alkylamines having about 1 to 18 carbon atoms, such as propylamine,butylamine, diethylamine, dipropylamine, etc. Examples of mono- ordi-alkanol monoamines are ethanolamine, propanolamine, diethanolamine,dipropanolamine, etc. Useful examples of other monoamines are piperdine,cyclohexylamine, pyrrolidine, morpholine, etc. Examples of polyaminesare ethylenediamine, hexamethylenediamine, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, propylenediamine,dipropylenetriamine, butylenediamine, N-aminoethanolamine,monoethylethylenediamine, diethylaminopropylamine,hydroxyethylaminopropylamine, monomethylaminopropylamine, piperazine,N-methylpiperazine, N-aminoethylpiperazine, etc. Particularlypreferrable are aliphatic mono- or polyamines having one secondary aminogroup, such as diethylamine, diethanolamine, diethylenetriamine,monoethylethylenediamine, hydroxyethylaminopropylamine, etc. Accordingto this invention, an aromatic amine can be used in combination with thealiphatic or alicyclic amine in such amount that the reaction product ofepxoy resin and basic amine, when neutralized with acid, will stillremain dispersible in water. Examples of useful aromatic amines areaniline, N-methylaniline, toluidine, benzylamine, m-xylylenediamine,m-phenylenediamine, 4,4'-diaminodiphenylmethane, etc. Use of sucharomatic amine achieves the effect of increasing resistances to waterand to corrosion of the coating film.

Of the above enumerated amines, diethanol amine is the most preferred.

The conditions of Reaction No. 2 are with or without an organic solventthat is non-reactive with each of the reactants and the products at atemperature ranging from 100° C. to 150° C. for a period of time rangingfrom about 1 to 3 hours. In general, one is interested in obtaining aproduct having all oxirane rings reacted.

It should also be appreciated that reaction sequences 1 and 2 may bereversed whereby the amine is reacted first with the oxirane rings andthen the remaining rings are reacted with the fatty acid. Care must betaken in this reaction sequence to prevent gellation due to the presenceof the tertiary amine which is the reaction product between the hydrogencontaining amine and the oxirane ring. The tertiary amine promotes thereaction between an oxirane ring and the hydroxyl group which may bepresent in the polymer reactant as well as the reaction products if theamine contains a hydroxyl group thereon.

There are a number of other configurations of the conjugated fatty acidester. The fatty acid may be reacted with a polyol as mentioned above.The fatty acid may also be reacted with glycidyl containing materialsprior to reaction sequence No. 1, including glycidyl acrylate ormethacrylate. Other epoxy or glycidyl containing materials are mono- orpolyepoxides, preferrably a polyepoxide having an epoxy equivalentgreater than 1, such as polyglycidyl ethers of polyphenols, such asbisphenol A. These can be prepared by etherification of a polyphenolwith epichlorohydrin in the presence of alkali.

Another quite useful class of polyepoxides are produced similarly fromnovolak resins or similar polyphenol resins.

Also suitable are the similar polyglycidyl ethers of polyhydric alcoholswhich may be derived from such polyhydric alcohols as ethylene glycol,diethylene glycol, triethylene glycol, 1,2-propylene glycol,1,4-propylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerol,bis(4-hydroxycyclohexyl) 2,2-propane and the like. There can also beused polyglycidyl esters of polycarboxylic acids, which are produced bythe reaction of epichlorohydrin or similar epoxy compounds with analiphatic or aromatic polycarboxylic acid such as oxalic acid, succinicacid, glutaric acid, terephthalic acid, 2,6-naphthylene dicarboxylicacid, dimerized linolenic acid and the like. Examples are glycidyladipate and glycidyl phthalate. Also useful are polyepoxides derivedfrom the epoxidation of an olefinically unsaturated alicyclic compound.Included are diepoxides comprising in part one or more monoepoxides.These polyepoxides are non-phenolic and are obtained by the epoxidationof alicyclic olefins; for example, by oxygen and selected metalcatalysts, by perbenzoic acids, by acetaldehyde monoperacetate, or byperacetic acid, and/or hydrogen peroxide. Among such polyepoxides arethe epoxy alicyclic ethers and esters which are well known in the art.

A particularly preferred class of products that may be used in thepresent case is the reaction product of reacting a fatty acid,conjugated or not conjugated, with compounds containing nitrogenheterocyclic rings of 5 or 6 members, said compounds also containing oneor more epoxy rings. The reaction product can be characterized as anepoxy fatty acid ester.

The nitrogen heterocyclic materials are generally available in the tradeand have been described in a number of patents as:

U.S. Pat. No. 3,391,097--EPOXY RESINS FROM 1,1'-METHYLENEBIS(5-SUBSTITUTED HYDANTOIN)

U.S. Pat. No. 3,814,775--3-GLYSIDYL-HYDANTOIN ISOCYANATES

U.S. Pat. No. 3,846,442--GLYCIDYL HYDANTOIN COMPOUNDS

U.S. Pat. No. 3,449,353--N,N'-DIGLYCIDYL HYDANTOINS

U.S. Pat. No. 3,542,803--N,N'-DIGLYCIDYL COMPOUNDS

U.S. Pat. No. 3,592,823--N,N'-DIGLYCIDYL COMPOUNDS

U.S. Pat. No. 3,620,983--β-METHYLGLYCIDYLISOCYANURATES

U.S. Pat. No. 3,679,681--DIGLYCIDYL ETHERS

U.S. Pat. No. 3,726,895--DIGLYCIDYL DERIVATIVES OF COMPOUNDS CONTAININGTWO N-HETEROCYCLIC RINGS

U.S. Pat. No. 3,772,326--DIGLYCIDYL COMPOUNDS OF MONOHYDROXALKYLHYDANTOINS

U.S. Pat. No. 3,778,439--BINUCLEAR N-HETEROCYCLIC POLYGLYCIDYL COMPOUNDS

U.S. Pat. No. 3,780,057--PYRAZOLONE PIGMENTS

U.S. Pat. No. 3,787,405--DIGLYCIDYL COMPOUNDS CONTAINING AN-DETEROCYCLIC RING

U.S. Pat. No. 3,808,226--POLYACRYLATES OF N-HETEROCYCLIC COMPOUNDS

U.S. Pat. No. 3,809,660--EPOXIDE RESIN MIXTURES OF HETEROCYCLICN,N'-DIGLYCIDYL COMPOUNTS

U.S. Pat. No. 3,809,696--DIGLYCIDYL COMPOUNDS CONTAINING TWON-HETEROCYCLIC RINGS

U.S. Pat. No. 3,821,242--DIGLYCIDYL ETHERS

U.S. Pat. No. 3,821,243--HETEROCYCLIC TRIGLYCIDYL COMPOUNDS

U.S. Pat. No. 3,828,045--DIGLYCIDYL ETHERS OF FIVE AND SIX MEMBEREDN-HETEROCYCLIC COMPOUNDS

U.S. Pat. No. 3,828,066--DIGLYCIDYLIMIDAZOLIDONES

U.S. Pat. No. 3,843,675--N-HETEROCYCLIC POLYGLYCIDYL COMPOUNDSCONTAINING ESTER GROUPS

U.S. Pat. No. 3,864,358--EPOXY-ACRYLIC ACID ESTERS

all of which are hereby incorporated by reference.

Preferred classes of compounds are: ##STR3## wherein R₇ is hydrogen or##STR4## R₈ and R₉ are independently selected from the group hydrogen,alkyl of 1 to 5 carbon atoms, phenyl, a saturated aliphatic ring of 5 to7 carbon atoms or together form a 5 to 7 member saturated carbocyclicring; or ##STR5##

Regardless of the manner of introducing the oxirane ring into thecoating resin, the amine reactant shown in reaction No. 2 is used in anamount such that all oxirane rings are reacted and that the coatingcomposition as used in the electrodeposition process has no oxiranerings.

In curing the coating composition of the present invention, it has beenfound highly desirable that nitrogenous containing cross-linking agentsbe employed in an effective curing amount. Generally the amount ofnitrogen containing material that is employed is sufficient to reactwith some or all of the hydroxyl groups present on the polymericmaterial or the number of hydroxyl groups present on Formula A containedin the polymeric material. If desired, the amount of fatty acidcontaining unsaturation may be increased to produce an air driedcomposition.

When a cross-linking agent is employed, it is preferred that a blockedisocyanate or a melamine type containing composition be used as thecross-linking agent. Other cross-linking agents may also be used such asurea formaldehyde, phenol formaldehyde, benzoguanamine, amideimide,polyamide, polybenzimidazole, and the like.

Suitable isocyanates that may be used in the present invention are asfollows:

propylene-1,2-diisocyanate,

butylene-1,2-diisocyanate,

butylene-1,3-diisocyanate,

hexamethylene diisocyanate,

octamethylene diisocyanate,

nonamethylene diisocyanate,

decamethylene diisocyanate,

2,11-diisocyano-dodecane and the like,

meta-phenylene diisocyanate,

para-phenylene diisocyanate,

toluene-2,4-diisocyanate,

toluene-2,6-diisocyanate,

xylene-2,4-diisocyanate,

xylene-2,6-diisocyanate,

dialkyl benzene diisocyanate, such as methylpropylbenzene diisocyanate,methylethylbenzene diisocyanate, and the like,

2-2'-biphenylene diisocyanate,

3,3-biphenylene diisocyanate,

4,4'-biphenylene diisocyanate,

3,3'-dimethyl-4,4'-biphenylene diisocyanate, and the like,

methylene-bis-(4-phenyl isocyanate),

ethylene-bis(4-phenyl isocyanate),

isopropylidene-bis-(4-phenyl isocyanate),

butylene-bis-(4-phenyl isocyanate),

hexafluoroisopropylidene-bis-(4-phenyl isocyanate), and the like,

2,2'-oxydiphenyl diisocyanate,

3,3'-oxydiphenyl diisocyanate,

4,4'-oxydiphenyl diisocyanate, and the like,

2,2'-ketodiphenyl diisocyanate,

3,3'-ketodiphenyl diisocyanate,

4,4'-ketodiphenyl diisocyanate,

2,2'-thiodiphenyl diisocyanate,

3,3'-thiodiphenyl diisocyanate,

4,4'-thiodiphenyl diisocyanate, and the like,

2,2'-sulfonediphenyl diisocyanate,

3,3'-sulfonediphenyl diisocyanate,

4,4'-sulfonediphenyl diisocyanate, and the like,

2,2'-methylene-bis-(cyclohexyl isocyanate),

3,3'-methylene-bis-(cyclohexyl isocyanate),

4,4'-methylene-bis-(cyclohexyl isocyanate),

4,4'-ethylene-bis-(cyclohexyl isocyanate),

4,4'-propylene-bis-cyclohexyl isocyanate),

bis-(para-isocyano-cyclohexyl) sulfide,

bis-(para-isocyano-cyclohexyl) sulfone,

bis-(para-isocyano-cyclohexyl) ether,

bis-(para-isocyano-cyclohexyl)diethyl silane,

bis-(para-isocyano-cyclohexyl) diphenyl silane,

bis-(para-isocyano-cyclohexyl) ethyl phosphine oxide,

bis-(para-isocyano-cyclohexyl)phenyl phosphine oxide,

bis-(para-isocyano-cyclohexyl) N-phenyl amine,

bis-(para-isocyano-cyclohexyl) N-methyl amine,

2,6-diisocyano-pyridine,

bis-(4-isocyano-phenyl) diethyl silane,

bis-(4-isocyano-phenyl) diphenyl silane,

dichloro-biphenylene diisocyanate, bis-(4-isocyanophenyl) ethylphosphine oxide,

bis-(4-isocyano-phenyl) phenyl phosphine oxide,

bis-(4-isocyano-phenyl)-N-phenyl amine,

bis-(4-isocyano-phenyl)-N-methyl amine,

3,3'-dimethyl-4,4'-diisocyano biphenyl,

3,3'-dimethoxy-biphenylene diisocyanate,

2,4-bis-(β-isocyano-t-butyl) toluene,

bis-(para-β-isocyano-t-butyl-phenyl) ether,

para-bis-(2-methyl-4-isocyano-phenyl) benzene,

para-bis-(1,1-dimethyl-5-amino-pentyl) benzene,

3,3'-diisocyano adamantane,

3,3'-diisocyano biadamantane,

3,3"-diisocyanoethyl-1,1'-biadamantane,

1,2-bis-(3-isocyano-propoxy) ethane,

1,2-dimethyl propylene diisocyanate,

3-methoxy-hexamethylene diisocyanate,

2,5-dimethyl heptamethylene diisocyanate,

5-methyl-nonamethylene diisocyanate,

1,4-diisocyano-cyclohexane,

1,2-diisocyano-octadecane,

2,5-diisocyano-1,3,4-oxadiazole,

OCN (CH₂)₃ O(CH₂)₂ O(CH₂)₃ NCO,

OCN (CH₂)₃ S(CH₂)₃ NCO, OCN (CH₂)₃ N(CH₂)₃ NCO,

polymethylene polyphenyl isocyanate; biurets of the formula ##STR6##where R¹⁰ is an alkylene group having 1-6 carbon atoms, especiallypreferred is the biuret of hexamethylene diisocyanate; ##STR7##

A number of blocking agents may also be used to produce a blockedisocyanate which could be used as the cross-linking agent. Such blockingagents as the phenol type, lactone type, active methylene type, alcoholtype, mercaptan type, acid amide type, the imide, the amine type, theurea type, carbamate type, oxime type, sulfate type and the like. Mostpreferrably a ketoxime type is preferred, and even more preferrably adialkyl ketoxime of from 1 to 4 carbon atoms per alkyl group. Mostpreferrably the ketoxime would be methylethyl ketoxime, methyl-isobutylketoxime, and the like.

Suitable melamine type cross-linking agents are hexamethoxymethylmelamine, alkylated (melamine-formaldehyde), butylated melamines, andthe like.

The coating compositions of the present invention are useful in thecathodic electrodeposition of substrates. Generally the bath pH rangesfrom about 3-9. The substrate may be any conductive substrate,preferrably iron, zinc or aluminum containing substrates such as steel,with or without protective coatings, such as phosphate corrosionresistant coatings. Most preferrably the coatings of the presentinvention are applied to metallic substrates such, as steel.

In the electrodeposition process, the conductive metallic substratewould be the cathode in the electrical process and an anode would beplaced in the electrodeposition bath, with the electrodeposition coatingof the present invention being incorporated in the aqueous electrolytebetween the anode and the cathode. The electrodeposition process is onethat would be conducted at a temperature ranging from about 50° F. to150° F., preferrably room temperature. The voltage may vary greatly,although normally it will operate between 50 and 500 volts. The currentdensity ranges from about 1 amp to about 15 amps per square foot.

The nitrogen containing coating compositions of the present inventionare solubilized, dispersed or suspended by means of an acid, such as anorganic acid, such as acetic acid, lactic acid, citric acid and thelike, although any water solubilizing agent may be used as boric orhydrochloric acid, etc.

As has been mentioned above, if a high concentration of unsaturatedfatty acids are employed, the composition may be air cured. Preferrably,however, the coating compositions are cured by means of subjecting thecoated substrate to a high temperature or a bank of infrared lampshaving a temperature ranging from about 250° F. (121° C.) to about 500°F. (260° C.), preferrably between about 300° F. (149° C.) and about 390°F. (199° C.) from a time ranging from about 1 minute to 1 hour,preferrably 10 minutes to 45 minutes.

It is to be appreciated that a curing catalyst may also be added to thecoating composition, such as tin compounds as dibutyl tin dilaurate,dibutyl tin diacetate, dibutyl tin oxide, metallic dryers as cobalt andzirconium, naphthenate or octoate.

When a blocked isocyanate is employed as described above, it is to beappreciated that the blocking agent will decompose at temperaturesgreater than 50° C. which will permit the remaining isocyanate moiety toreact with the film forming composition. At less than about 50° C., theblocked isocyanate is substantially stable and is nonreactive with thehydroxyl groups present on the acrylic polymer, or the hydroxyl groupspresent on Formula A moiety.

In known manner, catalysts, pigments, anti-oxidants, surfactants orfillers may be added to the coating composition to improve theappearance, texture, gloss and other properties of the cured film.Pigments such as carbon black, titanium dioxide, metal oxides,chromates, sulfates and the like may be used.

The components of the coating composition (on a pigment, filler andcatalyst free basis) of the present invention are generally present asfollows:

    ______________________________________                                        Resin          Range          Preferred                                       ______________________________________                                        Monomer (total)                                                                              about 30 to about 60                                                                         49                                              acrylic portion                                                                              about 10 to about 40                                                                         20                                              Fatty acid ester                                                                             about 30 to about 50                                                                         36                                              Formula A producing                                                                          balance        15                                              amine                                                                         TOTAL (parts by                                                                              100            100                                             weight)                                                                       Cross-linking Agent                                                                          about 10 to about 50                                                                         about 20 to                                                                   about 30                                        TOTAL (resin + cross-                                                                        100            100                                             linking agent)                                                                (parts by weight)                                                             ______________________________________                                    

Having described the invention in general, listed below are embodimentswherein all parts are in parts by weight and all temperatures in degreescentigrade, unless otherwise indicated.

EXAMPLE NO. 1

Into a beaker equipped with a thermometer, stirrer and reflux condenserwas placed dehydrated castor oil fatty acid (contains 30% conjugateddouble bonds; 329.4 parts), n-butyl glycidyl ether (132.6 parts) andzirconium octoate (0.5 parts) and heated under a nitrogen environment to150° and allowed to exotherm. The heat was held at 190° until an acidnumber of about 33. Then LSU 549 (trademark of Ciba Geigy for a productof the structure ##STR8## having a melting point of 90°-95° C. and anepoxy equivalent (Kg of 6.8; 55.9 parts) was added and temperature heldto an acid number of zero was reached. The mixture was cooled to 165° C.and over 1 7/8 hours was added styrene (413 parts), glycidylmethyacrylate (GMA) (287 parts) and dicumene peroxide catalyst (31parts) and then heated for an additional hour at 180°. The solution wascooked to 140° and di-tert-butyl peroxide (2.7 parts) was added. Theproduct was held to 96% theoretical solids content, cooled to 95° anddiethanolamine (202 parts) added. The mixture exothermed to 120° andtemperature held there for one hour. Thereafter n-butanol was added (254parts). The product had an amine value of 75.3 and a viscosity (25° C.;50% theoretical solids in n-butanol) of P (hereinafter product A).

A coating composition was formulated from the above product as follows:

Into a pebble mill was added carbon black (8 parts), product A (40parts) and n-butanol (32 parts) and ground for 40 hours until carbonblack is dispersed and has a Hegman reading of 7+. (hereinafter productB--pigment dispersion). Product A (311.3 parts), Cymel 1116 (trademarkof American Cyanamid for a melamine cross-linking agent)--(71.8 parts)and zirconium octoate (1.8 parts) was placed in a Cowles mixer and mixedwith barytes (40 parts) to a reading of Hegman 7+. Thereafter product B(80 parts) and acetic acid (12.3 parts) was mixed with product A and thecross-linking agent and emulsified with deionized water until aninversion occurs.

A zinc phosphate treated panel was used as a cathode and a carbon anodewith the coating composition described above (10% solids) as theelectrolyte. The voltage employed was 200 volts with the coatingthickness on the cathode ranging from 0.50-0.65 mils. The panel waswashed and baked at a temperature of 400° F. for 20 minutes. Smoothglossy films with good adherence to the metal substrates were obtainedwith satisfactory salt spray (5% sodium chloride in water) results.(Scribe pull of 2-6 mm. after 276 hours).

EXAMPLE NO. 2

Into a beaker equipped with a stirrer, thermometer and a refluxcondenser was placed Pamolyn 380 (trademark of Hercules for a conjugatedfatty acid being characterized as containing 70% conjugated unsaturationof linoleic acid, an acid number of 197, an iodine value of 102 and anoleic acid content of 22%; 224 parts; 0.8 equivalents); n-butanol (59parts; 0.8 equivalents). The mixture was heated under a nitrogen blanketto a temperature of 130° for about 6 hours, removing water to produce anacid number of zero to produce the butyl ester of Pamolyn 380.

In a separate equivalently equipped beaker was placed butyl ester ofPamolyn 380 (517.9 parts) and heated to 165° C. Over aone-hour-and-forty-five-minute period was added styrene (413 parts), GMA(287 parts) and dicumene peroxide (31 parts). Thereafter the mixture washeated at about 180° C. for another hour. The mixture was cooled to 140°C., and di-tert-butyl peroxide (2.7 parts) was added and mixture heldfor less than an hour at same temperature until theoretical solidsreached 96%. The mixture was cooled to 95° and diethanol amine (202parts) was added, the temperature heated to 125° C. for 2 hours.Thereafter n-butanol (254 parts) was added. The product had an aminevalue of 90.0 and a viscosity of m (25° C. in 50% theoretical solids inn-butanol).

What is claimed is:
 1. A method of electrocoating a film forming substance onto a substrate by employing an anode, a cathode and an electrolyte therebetween comprising the steps:(1) Providing an aqueous electrolyte containing an organic coating composition comprising a dispersion, solution or suspension of a coating composition characterized by:(a) the reaction product of a conjugated fatty acid ester and an acrylic containing monomer; and (b) Formula A within the molecule and being the reaction product of reacting an amine with an oxirane ring; wherein Formula A is:

    --CH.sub.2 --C(Z)--CH.sub.2 --N═

wherein Z is independently selected from the group consisting of hydrogen, hydroxyl, alkoxy of from one to 6 carbon atoms; acyloxy of from one to 6 carbon atoms; (═O),--OR'--_(n) H, --OR'--_(n) OH, and --OR'(CH₂ OH)--_(n) OH; wherein R' is a saturated alkylene of from 2 to 4 carbon atoms and n is a number from 1 to 6; (2) Closing the circuit between the anode and the cathode; and (3) Depositing the film forming composition onto the cathodic substrate.
 2. The method of claim 1 wherein the fatty acid ester is obtained by the reaction between a fatty acid and a polyol.
 3. The method of claim 1 wherein the composition is substantially free of oxirane rings.
 4. The method of claim 3 wherein Z is hydroxyl.
 5. The method of claim 1 further comprising an effective amount of a nitrogenous cross-linking composition.
 6. The method of claim 1 wherein the coating composition is comprised of a resin portion characterized as follows:

    ______________________________________                                         Components           Parts by Weight                                           ______________________________________                                         (a)   total monomer portion used                                                                        about 30 to about 60                                        to produce polymer                                                       (b)   fatty acid ester portion                                                                          about 30 to about 50                                  (c)   Formula A producing amine                                                                         balance                                                     portion                                                                  ______________________________________                                    

wherein the total resin components equals 100 parts (on a pigment, filler and catalyst free basis).
 7. The method of claim 1 wherein the acrylic monomer comprises about 10 to about 40% of the total resin portion of the coating composition.
 8. The method of claim 1 wherein Z is hydroxyl.
 9. An article produced according to the process of claim
 1. 10. The method of claim 1 wherein the reaction between the fatty acid ester and the acrylic containing monomer is a Diels-Alder reaction as the first step for preparing the coating composition and the second step is reacting said Diels-Alder reaction product with an alkanol amine. .Iadd.
 11. A method of electrocoating a film forming substance onto a substrate by employing an anode, a cathode and an electrolyte therebetween comprising the steps:(1) Providing an aqueous electrolyte containing an organic coating composition comprising a dispersion, solution or suspension of a coating composition characterized by:(a) the reaction product of a conjugated fatty acid ester and an acrylic containing monomer; and (b) Formula A' within the molecule and being the reaction product of reacting an amine with an oxirane ring, wherein Formula A' is: ##STR9##.Iaddend. wherein Z is independently selected from the group consisting of hydrogen, hydroxyl, alkoxy of from 1 to 6 carbon atoms; acyloxy of from 1 to 6 carbon atoms; (═O),--OR'--_(n) H, --OR'--_(n) OH and --OR'(CH₂ OH)--_(n) OH; wherein R' is a saturated alkylene group of from 2 to 4 carbon atoms and n is a number from 1 to 6; and wherein X is H or -C- provided that when X is -C-, then C-X is part of an alicylic ring structure; (2) Closing the circuit between the anode and the cathode; and (3) Depositing the film forming composition onto the cathodic substrate. 